Synthesis, structural and theoretical studies of dithiodiglycolamide compounds of palladium(ii)Electronic supplementary information (ESI) available. CCDC 1009937-1009939 for 4, 5 and 7. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4dt03814b
The reaction of palladium( ii ) halide with dithiodiglycolamide ligands yielded compounds of the type [PdX 2 L] (where X = Cl, L = (CH 2 SCH 2 CON i Pr 2 ) 2 ( 1 ); L = (CH 2 SCH 2 CON i Bu 2 ) 2 ( 2 ); L = (CH 2 SCH 2 CONBu 2 ) 2 ( 3 ); L = C 7 H 6 (SCH 2 CON i Bu 2 ) 2 ( 4 ); X = Br, L = (CH 2 SCH...
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| Main Authors | , , , , |
|---|---|
| Format | Journal Article |
| Language | English |
| Published |
23.06.2015
|
| Online Access | Get full text |
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| Summary: | The reaction of palladium(
ii
) halide with dithiodiglycolamide ligands yielded compounds of the type [PdX
2
L] (where X = Cl, L = (CH
2
SCH
2
CON
i
Pr
2
)
2
(
1
); L = (CH
2
SCH
2
CON
i
Bu
2
)
2
(
2
); L = (CH
2
SCH
2
CONBu
2
)
2
(
3
); L = C
7
H
6
(SCH
2
CON
i
Bu
2
)
2
(
4
); X = Br, L = (CH
2
SCH
2
CON
i
Bu
2
)
2
(
5
); X = I, L = (CH
2
SCH
2
CON
i
Bu
2
)
2
(
6
)), whereas palladium(
ii
) nitrate yielded compounds of the type [PdL
2
](NO
3
)
2
(where L = (CH
2
SCH
2
CON
i
Pr
2
)
2
(
7
); L = (CH
2
SCH
2
CON
i
Bu
2
)
2
(
8
)). All compounds were characterized by using IR,
1
H NMR spectral techniques and CHN analyses. The structures of compounds
4
,
5
and
7
have been determined by using X-ray diffraction methods. The structures show that the ligands bond through the thioether group to the metal centre in all compounds. They show further that the palladium(
ii
) ion is surrounded by four atoms (two halogens and two thio groups in
4
and
5
and four thio groups in
7
) in a square planar arrangement. The dithiodiglycolamide ligand acts as a bidentate chelating ligand and bonds through both the thioether groups to the metal centre, leaving the carbamoyl groups uncoordinated. Theoretical studies reveal that the 1 : 2 compound is energetically more stable and nicely correlates with the IR carbamoyl stretching frequencies as compared to the 1 : 1 compound in which the ligand acts as a tetradentate ligand.
The chemistry of dithiodiglycolamide with palladium(
ii
) halide and nitrate was studied by NMR, X-ray diffraction and theory. It is established that the bidentate chelating mode of bonding
via
thioether group is more stable than that of tetradentate mode. |
|---|---|
| Bibliography: | Electronic supplementary information (ESI) available. CCDC For ESI and crystallographic data in CIF or other electronic format see DOI 4 5 and 7 for 10.1039/c4dt03814b 1009937-1009939 , |
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/c4dt03814b |